Detergent compositions containing particle deposition enhancing agents



United States Patent O 3,489,686 DETERGENT COMPOSITIONS CONTAININGPARTICLE DEPOSITION ENHANCING AGENTS John J. Parr-an, Jr., SpringfieldTownship, Hamilton County, Ohio, assignor to The Procter & GambleCompany, Cincinnati, Ohio, a corporation of Ohio No Drawing.Continuation-impart of application Ser. No. 476,175, July 30, 1965. Thisapplication Dec. 11, 1967, Ser. No. 689,349

Int. Cl. Clld 3/48, 3/42, 3/26 U.S. Cl. 252-l06 10 Claims ABSTRACT OFTHE DISCLOSURE Detergent compositions containing water-insolubleparticulate substances, such as antimicrobial agents, and certainpolyethylenimine or alkoxylated polyethylenimine polymers which serve toenhance the deposition and retention of such particulate substances onsurfaces washed with the detergent composition.

CROSSREFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of the copending application of John J. Parran,Jr., Ser. No. 476,- 175, filed July 30, 1965, now abandoned.

BACKGROUND OF THE INVENTION The field of this invention is detergentcompositions including shampoos (liquid and cream), laundering,hardsurface and dishwashing detergents (granular and liquid), andpersonal use toilet detergent bars.

Various water-insoluble particulate substances have been incorporated indetergent products for the purpose of imparting some residual propertyor characteristic on surfaces washed with the products. For example,shampoo compositions containing particulate antidandruif agents havebeen developed which function by deposition and retention of theparticulate agent on the hair and scalp during shampooing. Sufficientquantities of the deposited particulate agents are retained afterrinsing to impart some degree of residual antimicrobial activity to thewashed hair and scalp. Such antidandruff shampoo compositions aredisclosed, for example, by Karsten, Taylor and Parran in US. Patent3,263,733, granted Feb. 22, 1966.

Particulate antimicrobial substances have also been used in variouslaundry detergents and personal use toilet detergent bars to impartresidual antimicrobial activity on the fabrics or skin surfaces washedwith same. Such products are disclosed by Reller and Jordan in US.Patents 3,134,711, granted May 26, 1964, and 3,256,200, granted June 14,1966.

Various other water-insoluble or sparingly soluble particulate materialssuch as sunscreens, fabric brighteners, and whiteners have been employedin detergent compositions and depend for their activity on particledeposition and retention on washed surfaces.

It is apparent that an effective detergent composition, properly used,will by its very nature tend to minimize retention of particulate matteron washed surfaces. Thus, only a relatively small proportion ofparticles present in such detergent compositions are actually retainedafter rinsing of the washed surface. Since the activity of antimicrobialand other particulate agents is in part a function of the quantity ofparticles deposited and retained on the involved surfaces, measureswhich enhance deposition and/or promote retention of such particlesserve to reduce the quantity of the substance in the compositionrequired to attain a given level of activity or increase the 3,489,685Patented Jan. 13, 1970 SUMMARY OF THE INVENTION It has now beendiscovered that polyethylenimine and alkoxylated polyethyleniminepolymers having a molecular weight within the range from about 2,000 toabout 3,000,000, and having a cationic charge density (as definedhereinafter) greater than .001 in aqueous solution, enhance thedeposition and retention of water-insoluble or sparingly solubleparticulate substances contained in detergent compositions on surfaceswashed therewith.

Although the mechanism whereby this phenomenon occurs is not fullyunderstood, it is believed that the polymer coats or attaches itself insome way on the involved particles imparting a net positive chargethereto which increases the affinity of the particle for the generallynegatively charged washed surfaces.

It is therefore an object of this invention to provide detergentcompositions which have improved capacities to impart residual activityor properties to surfaces washed therewith.

It is a further object of this invention to provide improved detergentcompositions containing water-insoluble or sparingly soluble particulatesubstances which are deposited and retained on washed surfaces.

It is yet another object of this invention to provide a method forenhancing the deposition of particulate substances from detergentcompositions and the retention of such substances on surfaces washedtherewith.

These and other objects will become apparent from the following detaileddescription of the invention.

DETAILED DESCRIPTION OF THE INVENTION The detergent compositions of thisinvention are comprised of (1) an organic surface active agent(surfactant, i.e., detergent compound); (2) a water-soluble cationicpolymer selected from the group consisting of polyethylenimine andalkoxylated polyethylenimine having a molecular weight within the rangefrom about 2,000 to about 3,000,000 and (3) a waterinsoluble orsparingly soluble particulate substance capable of imparting a desiredresidual property to a surface to which it becomes afiixed.

In its process aspect, this invention is a method for enhancing thedeposition and retention of particulate substances upon surfaces washedwith a detergent composition containing same, comprising uniformlyadmixing said particulate substances with a polyethylenimine oralkoxylated polyethylenimine polymer having a molecular weight withinthe range from about 2,000 to about 3,000,- 000, and having a cationiccharge density greater than .001 in aqueous solution, and incorporatingsaid mixture in a detergent base.

The cationic charge density of a polymer as that term is used hereinrefers to the ratio of the number of positive charges on a monomericunit of which the polymer is comprised to the molecular weight of saidmonomeric unit, i.e.,

number of positive charges monomeric unit molecular Weight cationiccharge density:

soluble salts of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 8 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester radical. Suchsurfactants include the sodium, potassium, and trienthauolamine alkylsulfates, especially those derived by sulfation of higher alcoholsproduced by reduction of tallow or coconut oil glycerides; sodium orpotassium alkyl benzene sulfonates, especially those of the typesdescribed by Gunther et al. in US. Patent 2,477,383, granted July 26,1949, in which the alkyl group contains from about 9 to about 15 carbonatoms; sodium alkyl glyceryl ether sulfonates, especially those ethersof higher alcohols obtained from tallow and coconut oil; sodium coconutoil fatty acid monoglyceride sulfates and sulfonates; sodium salts ofsulfuric acid esters of the reaction product of one mole of a higheralcohol (i.e., tallow or coconut oil alcohols) and about 3 moles ofethylene oxide; and the water-soluble salts of condensation products offatty acids with sarcosine, e.g., triethanolamine N-acyl sarcosinate,the acyl radicals being derived from coconut oil fatty acids.

Preferably, anionic organic surfactants of the high sudsing type areused for the shampoo embodiments of this invention. Thus, alkyl glycerylether sulfonates, N-acyl sarcosinates, and alkyl ether ethylene oxidesulfates as described above are used to special advantage. These and theforegoing surfactants can be used in the form of their sodium, potassiumor lower alkanolamine (e.g., mono, di, and triethanolamine) salts.

Conventional soaps are also operable anionic surfactants for thepurposes of this invention. Suitable soaps include the water-solublesalts, e.g., sodium, potassium, and lower alkanolamine salts of fattyacids occurring in coconut oil, soybean oil, castor oil or tallow, orsynthetically produced fatty acids may be used.

Polar nonionic surfactants can be used herein, either alone or inadmixture with anionic and/or ampholytic surfactants. Surfactants ofthis class can serve to enhance lathering and cleaning properties ofanionic detergents. By polar nonionic surfactant is meant a surfactantin which the hydrophilic group contains a semi-polar bond directlybetween two atoms, e.g., N- O, P O, As O, and S O. (The arrow is theconventional representation of a semi-polar bond.) There is chargeseparation between the two directly bonded atoms, but the surfactantmolecule bears no net charge and does not dissociate into ions.

A preferred polar nonionic surfactant for use in the presentcompositions is amine oxide of the general formula R R R N O, wherein Ris an alkyl, alkenyl, or monohydroxyalkyl radical having from about 10to 16 carbon atoms, and R and R are each methyl, ethyl, propyl, ethanolor propanol radials. An especially preferred amine oxide isdodecyldimethylamine oxide.

Other operable polar nonionic surfactants are the phosphine oxideshaving the general formula R R R P O, wherein R is an alkyl, alkenyl ormonohydroxyalkyl radical ranging in chain length from 10 to 18 carbonatoms, and R and R are each alkyl or monohydroxyalkyl radicalscontaining from 1 t 3 carbon atoms. A preferred phosphine oxide isdodecyldimethyl phosphine oxide.

Suitable amphoteric surfactants include the alkylbetaiminodipropionates, RN(C H COOM) alkyl beta-aminoproprionates,RN(H)C H COOM; and long chain imidazole derivatives having the generalformula:

OH CHzCOOM In each of the above formulae, R is an acyclic hydrophobicgroup containing from about 8 to about 18 carbon atoms and M is a cationto neutralize the charge of the anion, e.g., alkali metal such as sodiumand potassium and ammonium and substituted ammonium ca ions. Specificoperable amphoteric surfactants include the disodium salt oflauroyl-cycloimidinium-l-ethoxy-ethionic acid-2- ethionic acid, dodecylbeta-alanine, and the inner salt of Z-trimethylamino lauric acid. Aszwitterionics, the substituted betaines such as alkyl dimethyl ammoniaacetates wherein the alkyl radical contains from about 12 to about 18carbon atoms can also be used. Several examples of 7 this class ofzwitterionic surfactants are set forth in Canadian Patent 696,355,granted Oct. 20, 1964.

Especially preferred shampoo compositions in accordance with thisinvention will contain a non-soap anionic organic surfactant at aconcentration of from about 8% to about 30% by weight of the totalcomposition.

Although nonionic and cationic surfactants are not preferred for thepurposes of this invention they can nevertheless be used withoutsubstantial loss of the advantageous effects of the cationic polymers ondeposition and retention of particulate matter on washed surfaces.Nonionic surfactants may be described as compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature. As those skilled in the art are well aware, the length of thehydrophilic or polyoxyaklylene radical required for condensation withany particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

For example, a well known class of nonionics is made available on themarket under the trade name of Pluaronic. These compounds are formed bycondensing ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol. The hydrophobicportion of the molecule, of course, exhibits water insolubility. Themolecular weight of this portion is of the order of 950 to 4,000. Theaddition of polyoxyethylene radicals to this hydrophobic portion tendsto increase the water solubility of the molecule as a whole. Liquidproducts are obtained up to the point where polyoxyethylene content isabout 50% of the total weight of the condensation product.

Suitable nonionics also include the polyethylene oxide condensates ofalkyl phenols, e.g., the condensation products of alkyl phenols havingabout 6 to 12 carbon atoms, either straight chain or branch chain, inthe alkyl group with ethylene oxide in amounts equal to 10 to 25 molesof ethylene oxide per mole of alkyl phenol. The alkyl substituent insuch compounds may be derived from polymerized propylene, diisobutylene,octane, or nonane, for example.

Other suitable nonionics may be derived by the condensation of ethyleneoxide with the product resulting from the reaction of propylene oxideand ethylene diamine. Here again, a series of compounds may be produced,depending on the desired balance between hydrophobic and hydrophilicelements. For example, compounds (molecular weight from about 5,000 toabout 11,000) of about 40% to polyoxyethylene content and resulting fromthe reaction of ethylene oxide groups with a hydrophobic baseconstituted of the reaction product of ethylene diamine and excesspropylene oxide, said base having a molecular weight of the order .of2,500 to 3,000, are satisfactory.

Further satisfactory nonionics include the condensation product ofaliphatic alcohols having from 8 to 18 carbon atoms, either straightchain or branch chain, with ethylene oxide, an example being a coconutalcohol/ ethylene oxide condensate having from 10 to 30 moles ofethylene oxide per mole of coconut alcohol, the coconut alcohol fractionhaving from 10 to 14 carbon atoms.

Cationic surfactants which can be used in the compositions of thisinvention include distearyl dimethyl ammonium chloride, stearyl dimethylbenzyl ammonium chloride, coconut alkyl dimethyl benzyl ammonium chloraide, dicoconut alkyl dimethyl ammonium chloride, cetyl pyridiniumchloride, and cetyl trimethyl ammonium bromide.

As hereinbefore indicated, the compositions of this invention contain asan essential component a watersoluble cationic polyethylenimine oralkoxylated polyethylenimine polymer having a molecular weight withinthe range from about 2,000 to about 3,000,000 and a cationic chargedensity greater than .001 in aqueous solutlOIl.

It is believed that the structural formula of the backbone ofpolyethylenimine is:

HQC H l l CHgCH N OHZCHQNHZ H L l,

wherein x represents a whole number of sufficient magnitude to yield apolymer of molecular weight greater than about 2,000. Branch chainsoccur along the polymeric backbone and the relative proportions ofprimary, secondary and tertiary amino groups present in the polymer willvary, depending on the manner of preparation. The distribution of aminogroups in a typical polyethylenimine is approximately as follows:

The polyethylenimine is characterized herein in terms of molecularweight. Such polymers can be prepared, for example, by polymerizingethylenimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods are described in U.S. Patent Nos.2,182,306, Ulrich et al., granted Dec. 5, 1939; 3,033,746, Mayle et al.,granted May 8, 1962; 2,208,095, Esselmann et al., granted July 16, 1940;2,806,839, Crowther, granted Sept. 17, 1957; and 2,553,696, Wilson,granted May 21, 1951. Polyethylenimine has a cationic charge density of.004 in aqueous solution at pH 7.0.

Similarly, alkoxylated polyethylenimine can be prepared, for example, byreacting one part by weight ethylene oxide or propylene oxide with onepart by weight of polyethylenimine prepared as described above andhaving a molecular weight greater than about 2,000. Preferably, theweight ratio of polyethylenimine to alkylene oxide is at least about1:1. If this ratio is less than about 1:4 the cationic charge density ofthe polymer in aqueous solution will not be greater than .001 as isrequired for the purpose of this invention. Thus, the ratio ofpolyethylenimine to alkylene oxide must be equal to or greater thanabout 1:4. A preferred ethoxylated polyethylenimine has a molecularweight of about 80,000 to 120,000 and a cationic charge density of .004in aqueous solution at pH 7.0.

The cationic polymer can be employed herein at a concentration withinthe range from about 0.1% to about 10.0% by weight, preferably fromabout 0.25% to about 4.0% by weight.

Particulate substances which can be used in the detergent compositionsof this invention preferably have an average particle diameter withinthe range from about 0.2 to about 50 microns and include water-insolubleor sparingly soluble anti-microbial agents, sunscreens, fabricbrighteners, and various substances which create a favorable skin feelafter washing. These particulate substances depend on deposition andretention on washed surfaces to produce their intended effect.

Particulate antimicrobial substances, the deposition and retention ofwhich is enhanced by the cationic polymers described herein include, forexample, (a) substituted salicylanilidies having the general formula:

Y O H (H) Y Y .X Y

wherein X is hydrogen or halogen, and Y is hydrogen, halogen ortrifluoromethyl; (b) substituted carbanilides having the generalstructural formula:

wherein Y is hydrogen, halogen, or trifluoromethyl, X is halogen orethoxy, X is hydrogen or halogen; (c) substituted bisphenols having thegeneral structural formula:

wherein X is halogen and n is an integere from 1 to 3, R is an alkyleneradical having from 1 to 4 carbon atoms or divalent sulfur; and (d)mixtures of (a), (b), and (c).

The salicylanilides encompassed by (a) above include3,4,S-tribromosalicylanilide; 5bromosalicyl-3,5-di(trifluoromethyl)anilide; 5-chlorosalicyl 3,5di(trifluoromethyl)anilide; 3,5-dichlorosalicyl-3,4 dichloroanilide; and5-chlorosalicyl-3-trifiuoromethyl 4 chloranilide. These and othersalicylanilides useful herein are disclosed by Bindler and Model in US.Patent 2,703,332, granted Mar. 1, 1955.

The preferred cabanilides of (b) above include 3,4,4-trichlorocarbanilide; 3-trifluoromethyl 4,4 dichlorocarbanilide;3-trifluoromethyl-3',4,4-trichlorocarbanilide; 3,3-bis(trifluoromethyl)-4-ethoxy 4'-chlorocarbanilide; and 3,5 -bis(trifluoromethyl -4-chlorocarb anilide.

The compounds in (c) above in which R represents an alkylene radical aremore fully described in US. Letters Patent 2,555,077, granted Dec. 26,1950. The preferred compounds of the general class of (0) above arethose which are symmetrical in structural configuration, such as bis 5-chloro-2-hydroxy phenyl methane, bis (3 ,5 -dichloro 2-hydroxyphenyl)methane, bis 3,5 ,6-trichloro-2-hydroxyphenyl)methane, bis(3,5-dichloro2 hydroxyphenyl)- sulfide, bis(3,5,6-trichloro-2-hydroxyphenyl)sulfide,and mixtures thereof.

Additional antimicrobial compounds suitable for use in this inventionare N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboximide and N-l,l,2,2,-tetrachloroethylsulfenyl)-cis-A 4cyclohexene-1,2-dicarboximide.

Preferred antibacterial agents employed herein are salts ofZ-pyridinethiol-l-oxide which has the following structural formula intautomeric form, the sulfur being attached to the number 2 position ofthe pyridine ring:

2-pyridinethiol-1-oxide 1-hydroxy-2-pyridinethione Heavy metal salts ofthe above compounds are sparingly soluble and have a high degree ofantibacterial activity. Preferred salts include zinc, cadmium, tin andzirconium 2-pyridinethiol-1-oxide.

Combinations of the above-described antibacterial substances can also beused to advantage. Such combinations are illustrated in U.S. Patent3,281,366, granted Oct. 25, 1966.

These antimicrobial compounds are used in particulate form, with averageparticle sizes ranging from about 0.2 to about 30 microns. The quantityof antimicrobial agent employed can range from about 0.1% to about 10%and preferably from about 0.5% to about 2.0% 'by weight.

Preferred antimicrobial detergent compositions in accordance with thisinvention especially adapted to washing hair and scalp are comprised offrom about 10% to about 35% by weight of at least one non-soap anionic,polar nonionic, ampholytic or zwitterionic surfactant; from about 0.25%to about 2.0% by weight of a polyethylenimine or alkoxylatedpolyethylenimine polymer having a cationic charge density greater thanabout .001 and having an average molecular weight within the range fromabout 30,000 to about 1,000,000; from about 0.5% to about 2.0% by weightof a water-soluble or sparingly soluble antimicrobial substance inparticulate form; and the balance substantially water.

Detergent compositions in accordance with this invention can be preparedby methods well known in the art; however, as hereinbefore indicated, ithas been found that especially good results are obtained when thecationic polymer and particulate substances are uniformly admixed in aninitial step, with the mixture then being added to an aqueous solutionor slurry of the surfactant. If the polymeric component and particulatesubstance are added to the surfactant separately, the degree ofdeposition and retention enhancement effected by the polymer will besomewhat less.

Each of the aforementioned components can be incorporated in an aqueousvehicle which may, in addition, include such materials as organicsolvents, such as ethanol; thickeners, such as carboxymethylcellulose,magnesiumaluminum silicate, hydroxyethylcellulose or methylcellulose;perfumes; sequestering agents, such as tetrasodiumethylenediaminetetraacetate; and opacifiers, such as zinc stearate ormagnesium stearate, which are useful in enhancing the appearance orcosmetic properties of the product.

Coconut acyl monoor diethanol amides as suds boosters, and stronglyionizing salts such as sodium chloride and sodium sulfate may be used toadvantage.

Toilet detergent or soap bars containing a cationic polymer andparticulate substance according to this invention can be based on soapor non-soap synthetic detergents and can also contain a variety ofadjuvants to improve product performance or appearance. Examples of suchadjuvants include free fatty acids or cold cream to improve cosmeticproperties, perfumes, inorganic salts to improve bar firmness, insolublesoap to improve bar texture, coloring matter and the like.

In the case of heavy-duty laundering detergents containing the cationicpolymers and particulate substances in accordance with this invention,such detergents can be in granular, flake, liquid or tablet form and cancontain, in addition to detergent and inorganic or organic buildercompounds (such as those disclosed by Diehl in US. Patent 3,159,581,granted Dec. 1, 1964), minor amounts of adjuvant materials which makethe product more effective or more attractive. The following arementioned by way of example. A tarnish inhibitor such as benzotriazoleor ethylenethiourea may also be added in amounts up to about 2%.Fluorescers, perfume and color while not essential in the compositionsof the invention, can be added in amounts up to about 1%. An alkalinematerial or alkali, such as sodium hydroxide or potassium hydroxide, canbe added in minor amounts as supplementary pH adjusters when needed.There can also be mentioned as suitable additives, brightening agents,sodium sulfate, and sodium carbonate.

Corrosion inhibitors generally are also added. Soluble silicates arehighly effective inhibitors and can be added to certain formulas of thisinvention at levels of from about 3% to about 8%. Alkali metal,preferably potassium or sodium, silicates having a weight ratio ofSIOziMgO of from 1.0:1 to 28:1 can advantageously be used. M in thisratio refers to sodium or potassium. A sodium silicate having a ratio ofSiO :Na O of about 1.6:1 to 2.45:1 is especially preferred for economyand eifectiveness.

In the embodiment of this invention which provides for a built liquiddetergent, a hydrotropic agent at times is found desirable. Suitablehydrotropes are water-soluble Sodium coconut alkyl alkali metal salts oftoluenesulfonate, benzenesulfonate, and xylenesulfonate. The preferredhydrotropes are the potassium or sodium toluenesulfonates. Thehydrotrope salt can be added, if desired, at levels of 1% to about 12%.While a hydrotrope will not ordinarily be found necessary, it can beadded if so desired, for any reason including the preparation of aproduct which retains its homogeneity at a low temperature.

The term coconut alkyl as used herein and in the following examplesrefers to alkyl groups which are derived from the middle cut of coconutalcohol having the following approximate chain length distribution: 2% C66% C 23% C and 9%. C Other compounds designated as coconut oil derivedare based on unfractionated coconut oil or its fatty acids.

The following examples are illustrative of several detergentcompositions of this invention.

EXAMPLE I A shampoo composition was prepared having the followingcomposition:

Parts by wt. glyceryl ether sulfonate (about 23% diglyceryl and thebalance substantially monoglyceryl) 25.0 Sodium tallow alkyl glycerylether sulfonate (about 23% diglyceryl and the balance substantiallymonoglyceryl; the tallow alkyls correspond to those of substantiallysaturated tallow alcohols and contain approximately 2% C 32%C and 66% C3.0 Sodium chloride 6.7 Sodium sulfate 3.3 Sodium N-lauroyl sarcosinate3.8 N-coconut acyl sarcosine 1.2 Diethanolamide of coconut fatty acids2.0 Acetylated lanolin 1.0 Perfume 0.4 Color 0.04 Zinc2-pyridinethiol-1-oxide 2.0 Polyethyleniminc/ethylene oxide reactionproduct weight ratio 1:1, molecular weight 550,000-120,000

and cationic charge density of .004 in aqueous solution at pH 7.0 0.5Water Balance 1 Average particle size 2 microns.

The zinc pyridinethione and ethoxylated polyethylenimine were uniformlyadmixed and added to and uniformly mixed with the balance of thecomponents. The resulting product was a stable cream having excellentcosmetic and antidandruff properties. The degree of deposition of zincpyridinethione from this composition was much greater than the degree ofdeposition attained with a similarly formulated product which containedno cationic polymer. Residual antimicrobial activity of surfaces washedwith this composition is markedly greater as compared to surfaces washedwith a control product without polymer.

Compositions identical to the composition of Example I, but containing 5micron diameter particles of 3,4,4-trichlorocarbanilide;3,4,5-tribromosalicylanilide; 4,4-dichloro 3(trifluorornethyl)carbanilide; bis(2-hydroxy-3,5,6-trichlorophenyl)methane, and 6.5 micron particles ofN-trichloromethylmercapto-4-cyclohexene-1,2 dicarboximide andN-(1,1,2,2-tetrachloroethylsulfenyl)-cis-A-4-cyclohexene-1,2-dicarboximide, respectively, in place of zincZ-pyridinethiol-l-oxide are prepared and compared with controlcompositions containing these same compounds without cationic polymer.The degree of deposition and retention of these compounds in thepresence of the cationic polymer is found to be substantially greaterthan is attached with the control compositions, and a correspondingincrease in residual antimicrobial activity is observed on surfaceswashed therewith.

9 EXAMPLE II Another antimicrobial detergent formulation in accordancewith this invention is formulated as follows:

Parts by wt. Triethanolamine coconut alkyl sulfate 10.0 Coconut alkyldimethyl amine oxide 10.0 Monoethanol amide of coconut fatty acids 5.0Ethanol 10.0 Polyethylenimine 1 0.75

Cadmium Z-pyridinethiol-l-oxide (average particle size 3.0 microns) 0.25Water, NaOH to adjust to pH 8.5 Balance A water-soluble cationic polymerhaving a molecular weight of 50,000 to 100,000, a cationic chargedensity of .004 in aqueous solution at pH 7.0, and a viscosity of 2.5centipoise (absolute viscosity) in a 1% by weight aqueous solutionmeasured with an Ostwald viscosimeter at 100 F.

EXAMPLE III A liquid detergent composition suitable for use as anantidandruif shampoo is formulated as follows:

Parts by wt. Triethanolamine coconut alkyl sulfate 20.0 Monoethanolamide of coconut fatty acid 4.5 Magnesium aluminum silicate 0.9Methylcellulose 0.23 Dye 0.008 Perfume 0.8 Zinc 2-pyridinethiol-1-oxide1 1.0

Polyethylenimine/ethylene oxide reaction product (weight ratio 4:1;molecular weight 50,000; cationic charge density .004 in aqueoussolution at pH 7.0) 0.5 Water Balance 1 Average particle size 1.5microns.

This composition provides a substantial degree of antidandrulf effectwhen used in the customary fashion. The degree of deposiiton andretention of particulate zinc pyridine thione on the hair and scalpafter shampooing with this product is substantially greater than isattained with a similar composition without the polyethylenimine/ethylene oxide reaction product.

Each of the above compositions impart a residual antimicrobial activityto surfaces washed therein which is substantially greater than isattainable with similar compositions without the polymeric component.

In Example XI, distearyl dimethyl ammonium chloride, stearyl dimethylbenzyl ammonium chloride, or dicoconut alkyl dimethyl ammonium chloridecan be used in place or sodium dodecyl benzene sulfonate without loss ofthe improved deposition and retention of zirconium2-pyridinethiol-l-oxide particles effected by the polyethylen- 1m1ne.

In Example IV, sodium coconut alkyl (ethoxy) sulfate can be replacedwith the condensation product of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol andhaving a molecular weight of 1600 or the condensation product of octylphenol and ethylene oxide using a mole ratio of 1:15, with substantiallyequivalent results.

The enhanced deposition and retention of pyridinethione salts wasdemonstrated as follows: A control composition was formulated as inExample I, but omitting the polyethylenimine/ ethylene oxide reactionproduct. A composition similar in formulation but containing 0.5% ofpolyethylenimine having a cationic charge density of .004 in aqueoussolution at pH 7.0 and a molecular weight of 50,000 was prepared anddesignated test composition A. A test composition designated B whichdiffered from the control composition in containing 0.5 of thepolyethylenimine of composition A and 1.0% of zinc2-pyridinethiol-l-oxide having an average particle size of 2 microns,rather than 2.0% of this latter component as in the control composition,was also prepared.

The hair of 16 female subjects was shampooed by experienced beauty shopoperators who washed half of the hair and scalp of each subject with thecontrol composition. The other half of the subjects hair and scalp waswashed in the assigned test composition. The test and controlcomposition were used ad libitum, in quantities suflicient to provide agood lather. After lathering for 45 seconds, the hair was rinsed and thecompositions were reapplied, lathered for 45 seconds and rinsed again.The hair was then dried. A sample of cornified epithelium from both thecontrol and test halves of each subjects scalp was obtained by applyingcellulose adhesive tape against the scalp. The tape was then placed on aglass slide with the adhesive in contact with the glass. The slide wasexamined with a polarizing microscope at approximately 400 diameterswith polaroids crossed. While the cornified epithelium exhibited somedegree of birefringence, the highly anisotropic properties of theparticulate zinc Z-pyridinethiol-l-oxide made it readily visible undersuch viewing conditions. The relative quantity of particulate zinc2-pyridinethiol-1oxide was then graded Examples IV V VI VII VIII IX X XISodium coconut alkyl (ethoxy) sulfate 20 7. 5

Sodium lauroyl sarcosinate Sodium dodecyl benzene sulfonate-2-trimethylamine lauric acid Triethanolamine coconut alkyl mon glyceridesultonate Potassium coconut soap- Ethanol Polyethylenirnine 1Polyethylenimine/propylene oxide reaction product 2 Tin2-pyridine-thiol-l-oxide (average particle size 7 microns) ZirconiumZ-pyridinethiol-l-oxide (average particle size 4 microns) Water Balancel 2 (Molecular weight 10,000; cationic charge density .004 in aqueoussolution at pH 7.0.)

(Weight ratio 2:1; molecular weight 30,000; cationic charge densitygreater than .001 in aqueous solution at pH 7.0.)

on a to 4 scale, with a grade of 4 indicating heavy deposition, and 0indicating substantially no deposition.

The following results were obtained.

TABLE 1 Composition: Average degree of deposition Control 2.3

It can be seen from the above results that deposition and retention ofzinc Z-pyridinethiol-l-oxide was substantially greater from a detergentcomposition which contained 0.5% of polyethylenimine as compared to thecontrol composition which contained the same amount of zincZ-pyridinethiol-l-oxide without polymer. Similarly, composition B whichcontained only 1.0% of zinc 2- pyridinethiol-l-oxide yielded a somewhathigher degree of deposition and retention than the control compositionwhich contained twice as much of this salt, but no polymer.

In like manner the relative deposition of zinc 2-pyridinethiol-l-oxidefrom a detergent composition containing various concentrations ofethoxylated polyethylenimine was demonstrated as follows: The followingcompositions were prepared.

TABLE 2 Parts by Weight Composition Control C Sodium coconut alkylglyceryl ether sulfonate 1 25.0 Sodium tallow alkyl glyceryl ethersulfonate Sodium chloride. Sodium sulfate So dium N-lauroyl sarcosinate-N -coconut acyl sarcosinate Coconut acyl diethanolamide Acetylatedlanolin Zinc 2-pyridinethiol-l-oxide (average particle size 2 microns)Polyethylenimine/ethylene oxide reaction product 1 Water 1. 0 Balance 1Same as Example I.

Each of the compositions was tested in the manner described supra, usinga test composition and control composition on each of the test subjects.The results attained were as follows:

Average degree of deposition It can be seen that the degree ofdeposition attained with composition C containing only half as much zinc2- pyridinethiol-l-oxide as the control was yet greater than thecontrol. Composition D, which contains 1.0% polymer and only A as muchzine Z-pyridinethiol-l-oxide as the control, displayed only moderatelyless deposition than the control. Composition E, which contains 2%polymer and only half as much zinc 2-pyridinethiol-l-oxide as thecontrol, provides somewhat greater deposition than the control.Composition F, containing 2.0% polymer and only Mr as much zincZ-pyridinethiol-l-oxide as the control, provides a degree of depositionapproximately equal to the control.

EXAMPLE XII An antimicrobial milled toilet detergent bar which alsoconstitutes a preferred embodiment of this invention is prepared inaccordance with methods well known in the art and having the followingcomposition:

Parts by wt. Sodium alkyl glyceryl ether sulfonate 1 8.0 Potassium alkylsulfate 1 20.0 Magnesium soap of :20 tallow: coconut fatty acids 16.7Sodium soap of 89:20 tallow: coconut fatty acids 32.4 Inorganic salts(sodium and potassium chlorides and sulfates) 9.23,4,S-tribromosalicylanilide (average particle size 5 microns) 1.0Polyethylenimine 2 2.0 Water and miscellaneous 10.7

1 Alkyl groups derived from middle cut of alcohols obtained by catalyticreduction of coconut alcohol which has a chain length distributionsubstantially as follows: 2% C10, 66% C12, 23% C14, and 9% C16.

2 Molecular weight 50,000cati0nic charge density .004 in aqueoussolution at pH 7.0.

The deposition and retention of the particulate antimicrobial agent3,4,S-tribromosalicylanilide upon skin washed with the above compositionis substantially greater than occurs with a control composition withoutcationic polymer.

Toilet detergent bars identical in composition to the bar describedabove are prepared, replacing the 3,4',5- tribromosalicylanilide with 4micron particles of the antimicrobial agents 3,4,4-trichlorocarbanilide; 4,4'- dichloro 3 (trifluoromethyl)carbanilide;bis(2-hydroxy- 3,5,6 trichlorophenyl)methane; and a 1:1 mixture of 4,4dichloro 3 (trifluoromethyl)carbanilide and 3, 4',5tribromosalicylanilide, respectively, with improved deposition andretention of the antimicrobial particles being attained in each caserelative to control compositions without polyethylenimine.

EXAMPLE XIII An antimicrobial granular built laundry detergent productis prepared by conventional means, having the following compositionParts by wt. Sodium alkyl benzene sulfonate (the alkyl group averagingabout 12 carbon atoms and being de- 1 See Footnote 2, Example XII.

Each of the foregoing examples describe embodiments of this inventionwhich involve antimicrobial particulate substances. As hereinbeforedisclosed, the deposition and retention of other particulate substancesare also enhanced by the cationic polymers. The following examples areillustrative of detergent compositions in accordance with this inventioncontaining representative particulate substances which function throughdeposition and retention on washed surfaces.

Toilet detergent bars desirably contain a sunscreen or ultravioletabsorber which will deposit on the skin in the course of washingtherewith to provide protection against harmful sun rays. Suitableparticulate ultraviolet absorbers which can be incorporated in detergentbars for this purpose include, for example,2-hydroxy-4-noctoxybenzophenone, 2 hydroxy 4 methoxy2-carboxybenzophenone, and 2 hydroxy 4 methoxybenzophenone. Thesematerials are insoluble particulate solids which are employed in barsoap formulations in con- 13 centrations ranging from about 1% to aboutby weight.

EXAMPLE XIV A toilet soap bar containing an ultraviolet absorber isformulated in accordance with this invention as follows: Percent by wt.

Sodium soap of 50:50 talowzcoconut fatty acids 73.19

Coconut fatty acid 7.30 Cold cream 1.10 Inorganic salts (sodium chlorideand sulfate and silicate solids) 0.87 Perfume 1.232-hydroxy-4-n-octoxybenzophenone (particle size microns) 2.50 Cationicpolymer 1 3.00 Miscellaneous 0.81 Water 10.00

1 Same as Example III.

When used in the customary fashion, the toilet soap bar of this exampleeffects a substantially greater degree of deposition and retention ofthe particulate ultraviolet absorber (2-hydroxy-4-n-octoxybenzophenone)on the washed skin surfaces than does an identical composition withoutpolymer.

Additional toilet soap bars are prepared as above but containing2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2 hydroxy 4methoxybenzophenone, respectively, in place of2-hydroxy-4-n-octoxybenzophenone, with substantially equivalent results.

Other insoluble particulate substances which are desirably incorporatedin toilet soap or detergent bars include the so-called skin feelenhancers. Such materials are deposited as particles on the skin in thecourse of washing and create a favorable skin feel after washing. Suchmaterials include, for example, nicotinic acid, talc and silicones, suchas Dow-Corning silicone F-157. These materials are desirablyincorporated in a toilet bar formula at levels of about 10% by weight.

EXAMPLE XV A bar soap formulation as set forth in Example XIV isprepared substituting 10.2% by weight of nicotinic acid particles(average particle size 5 microns) for the 2- hydroxy 4 noctoxybenzophenone and coconut fatty acid. The resulting compositionyields a substantially greater degree of deposition and retention ofnicotinic acid particles on skin washed with the bar than is attainedwith a bar similarly formulated but without cationic polymer. Similarresults are obtained when Dow-Corning silicone F-l57 is used in place ofnicotinic acid.

Various insoluble fabric whiteners or brighteners, such as fluorescentdyes and bluings, e.g., ultramarine blue, deposit as particles onfabrics washed with laundry detergent products containing same. Suchmaterials can be used in heavy-duty laundry detergent products inconcentrations up to about 1% by weight.

EXAMPLE XVI A built liquid detergent formulation containing aparticulate bluing material and a cationic polymer in accordance withthis invention is formulated as follows:

Percent by wt. 3 (N,N-dimethyl-N-coconutammonio)-2hydroxypropane-l-sulfonate 9.00 Tergitol 12-P-12 (condensation productof 12 moles of ethylene oxide and one mole of dodecylphenol) 3.00

Tripotassium methylene diphosphonate 26.00

Water Balance 1 Same as Example I.

The above composition when used to launder white fabrics in theconventional method results in the deposition and retention ofsubstantially greater quantities of the ultramarine blue particles onthe washed fabrics than occurs when a product similarly formulated butwithout cationic polymer is used.

It will be obvious to those skilled in the art that the concept of thisinvention is applicable to a wide variety of insoluble or sparinglysoluble particulate substances in addition to those specificallydescribed in the foregoing specification. For example, perfumes whichhave been adsorbed on insoluble particulate resinous substances can bedeposited on skin, fabrics and other surfaces washed with detergentcompositions containing same to a substantially greater degree, throughthe inclusion in said compositions of a cationic polymer as hereindefined.

What is claimed is:

1. A detergent composition consisting essentially of (1) from about 2.0%to about 95.0% by weight of a Water-soluble organic detergent selectedfrom the group consisting of ampholytic, zwitterionic, anionic and polarnonionic detergents; (2) from about 0.1% to about 10.0% by weight of awater-soluble cationic polymer selected from the group consisting ofpolyethylenimine and the reaction product of polyethylenimine andethylene oxide or propylene oxide in a weight ratio greater than about1:4, said polymer having a molecular weight within the range from about2,000 to 3,000,000 and a cationic charge density greater than about .001in aqueous solution at pH 7.0; and (3) from about 0.1% to about 10.0% byweight of a water-insoluble or sparingly soluble particulate memberselected from the group consisting of antimicrobial, ultravioletabsorbent and fluorescent bluing substances, said substance having anaverage particle diameter within the range from about 0.2 to about 50microns.

2. The composition of claim 1 wherein the cationic polymer ispolyethylenimine having an average molecular weight within the rangefrom about 10,000 to about 100,000.

3. The composition of claim 1 wherein the cationic polymer is a reactionproduct of polyethylenimine having an average molecular weight greaterthan about 2,000 and ethylene oxide, said reaction product having anaverage molecular weight within the range from about 80,000 to about120,000, the weight ratio of polyethylenimine to ethylene oxide beingfrom about 1:1 to about 4:1.

4. The composition of claim 1 wherein the particulate substance is the2-pyridinethiol-1-oxide salt of a heavy metal selected from the groupconsisting of zinc, cadmium, tin and zirconium.

5. The composition of claim 1 wherein the particulate substance is3,4,4trichlorocarbanilide.

6. The composition of claim 1 wherein the particulate substance is3,4',S-tribrornosalicylanilide.

7. The composition of claim 1 wherein the particulate substance is4,4'-dichloro-3-(trifluoromethyl)carbanilide.

8. The composition of claim 1 wherein the particulate substance isbis(2-hydroxy-3,5,6-trichlorophenyl)methane.

9. A detergent composition consisting essentially of 1) from about 2% toabout of a Water-soluble anionic organic detergent; (2) from about 0.25%to about 4.0% of a water-soluble cationic polymer selected from thegroup consisting of polyethylenimine and the reaction product ofpolyethylenimine and ethylene oxide or propylene oxide in a weight ratioof from about 1:1 to about 4:1, said polymer having a molecular weightwithin the range from about 10,000 to about 100,000; and (3) from about0.1% to about 10.0% of a water-insoluble or sparingly solubleparticulate member selected from the group consisting of antimicrobial,ultraviolet absorbent, and fluorescent bluing substances, saidparticulate substance having an average particle diameter within therange from about 0.2 to 30 microns.

10. The composition of claim 9 wherein the particulate substance is anantimicrobial agent selected from the group consisting of zinc2-pyridinethiol-1-oxide, 3,4,4-

References Cited UNITED STATES PATENTS Judge et a] 167-87 X 10 Karstenet a1. 167-87 Dickson et a1. 252-82 Hofiman et a1. 252-107 X Casely252-107 X Huggins 252-106 15 1 6 3,355,388 11/1967 Karsten 252-1073,349,033 10/1967 Zuccarelli 252-106 X 3,400,198 9/1968 Lang 252-152 XFOREIGN PATENTS 769,273 3/1957 Great Britain. 782,322 9/1957 GreatBritain.

LEON D, ROSDOL, Primary Examiner M. HALPERN, Assistant Examiner US. Cl.X.R.

